Monoazo dyestuffs containing an acetylamino 2,4-dioxo-1,2,3,4-tetrahydroquinazoline

ABSTRACT

WATER-INSOLUBLE MONOAZO DYESTUFFS OF THE GENERAL FORMULA   1-R2,6-((2,5-DI(R2-O-),4-(R1-NH-SO2-)PHENYL)-N=N-CH(-CO-   CH3)-CO-NH-)-1,2,3,4-TETRAHYDROQUINAZOLINE-2,4-DIONE   WHEREIN R1 IS HYDROGEN, LOWER ALKYL, ARYL, ARALKYL OR CYCLOALKYL, WHICH MAY BE SUBSTITUTED BY LOWER ALKYL OR HALOGEN, R2 IS LOWER ALKYL, R3 IS HYDROGEN OR LOWER ALKYL AND A IS A BENZENE NUCLEUS SUBSTITUTED BY LOWER ALKYL, LOWER ALKOXY ON HALOGEN. SAID PIGMENTS CAN BE USED, FOR EXAMPLE, FOR DYEING OR PRINTING PLASTICS, CAOUTCHOUC, NATURAL AND SYNTHETIC RESINS TEXTILE FIBROUS MATERIALS OR PAPER. FUTHERMORE THEY CAN 12BE EMPLOYED FOR THE PREPARATION OF PRINTING INKS, LACQUERS AND DISPERSION PAINTS. THE NOVEL PIGMENTS POSSESS GOOD TO VERY GOOD FASTNESS PROPERTIES.

United States Patent 3,711,461 MONOAZO DYESTUFFS CONTAINING AN ACE-TYLAMINO 2,4 DIOXO 1,2,3,4-TETRAI-IYDRO- QUINAZOLINE Wolfgang Pretzer,Kelkheim, Taunus, and Joachim Ribka, Oifenbach (Main), Germany,assiguors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius& Bruning, Frankfurt am Main, Germany N0 Drawing. Filed Nov. 3, 1970,Ser. No. 86,634 Claims priority, application Germany, Nov. 6, 1969, P 1955 808.8 Int. Cl. C09b 29/36 US. Cl. 260-454 7 Claims ABSTRACT OF THEDISCLOSURE Water-insoluble monoazo dyestuffs of the general formula OCH:0R2

The present invention relates to new valuable waterinsoluble monoazodyestulfs of the general formula in which R is hydrogen, alkyl having 1to 4 carbon atoms, cycloalkyl which may be substituted, aryl or aralkyl,R is alkyl having -1 to 4 carbon atoms and R is hydrogen or alkyl having1 to 4 carbon atoms, and A is a benzene nucleus which may be substitutedby lower alkyl or alkoxy or halogen.

This invention, moreover, relates to a process for preparing thesedyestuffs, which comprises coupling diazonium compounds of1-amino-2,5-dialkoxybenzene-4-sulfonic acid amides of the generalformula JLNH CHaCOCHzCONH in which R R R and A have the meaning givenabove.

The diazo components may be prepared by 'known methods, for example byreacting 1-acetamino-2,5-dialkoxy-benzene-4-sulfonic acid chlorides withamines of the general formula R NH which are free from -SO H and COOHgroups. R NH may stand for ammonia, an aliphatic amine, such asmethylamine, ethylamine, npropylamine, i-propylamine, n-butylamine,i-butylamine, a cycloalkylamine which may be substituted by halogen oralkyl, for example cyclohexylamine, Z-methylcyclohexylamine,2,4-dimethylcyclohexylamine, 2-chlorocyclohexylamine,2-chloro-3-methylcyclohexylamine or an aryl or aralkylamine, preferablyof the benzene or naphthalene series, which may be substituted byhalogen, alkyl, phenyl, alkoxy, phenoxy, nitro, trifluoromethyl,alkylsulfonyl, arylsulfonyl or aral-kylsnlfonyl. Such aromatic aminesmay, for example, be aniline, chloro-anilines, such as 2-chloroaniline,3-chlor0aniline or 4-chl0roaniline, dichloroanilines, such as2,4-dichloroaniline or 2,5-dichloroaniline, trichloroanilines, such as2,4,5-trichloroaniline or 2,4,6-trichloroaniline, monoanddibromoanilines, such as 2-bromoaniline or 2,4-dibromoaniline,toluidines, such as 2-methylaniline, 3-methylaniline or 4-methylaniline,xylidines, such as 2,3-dimethylaniline, 2,4-dimethylaniline or3,5-dimethylaniline, anisidines, such as Z-methoxyaniline, 3 methoxyaniline or 4 methoxy aniline, 2,5-dimethoxyaniline, 4-amino-diphenylether, nitro-anilines, such as 2-nitro-aniline, 3-nitro-aniline or4-nitro-aniline, Z-trifluoro-methylaniline,3,S-bis-trifluoromethylaniline, 4- aminophenyl ethyl sulfone, 4aminophenylsulfone, 1- amino-naphthalene, Z-amino-naphthalene as Well asaromatic amines having different substituents, such as 5- chloro 2methylaniline, 4 chloro 2 methylaniline, 4- chloro 2 methoxyaniline,S-chloro-Z-methoxyaniline, 5- chloro-2,4-dimethoxyaniline, 4chloro-2,5-dimethoxyaniline, 4-methoxy-Zanethylaniline,5-methyl-4-chloro-2-methoxyaniline, 2-chloro 4 nitro-aniline,4-chloro-2-nitroaniline, 5-nitro-2-methylaniline,2-nitro-4-methylaniline, 4 nitro 2 methoxyaniline,2-nitro-4-methoxyaniline, 4- chloro-3-trifluoromethylaniline, 2amino-4-trifluoromethylphenyl-benzylsulfone, benzylamine,4-nitrobenzylamine, S-chloro-2-methoXy-benzylamine, 4-aminobenzonitrileand 4-amino-diphenyl. In this manner, 1-acetamino-2,5-dialkoxybenzene-4-sulfonic acid amides are obtained from which the desired diazocomponents 1-amino-2,5-dialkoxybenzene-4-sulfonic acid amides areprepared by saponification of the acetamino group.

The coupling components can also be prepared by known methods, forexample, by reacting 2-ch1oro-5-nitrobenzoic acid with amines of thegeneral formula R NH at elevated temperature, optionally under pressure.Instead of 2-chloro-5-nitrobenz0ic acid, the compound substituted byalkyl or alkoxy or further halogen atoms can be reacted in acorresponding manner with the amines R NH Such amines R NH may beammonia or aliphatic amines, for example methylamine, ethylamine,n-propylamine, i-propylamine, n-butylamine, i-butylamine. Theproductsobtained, i.e. 2-amin0-5-nitrobenzoic acid or 2-alkylamino-5-nitro-benzoic acids, are reacted withv alkali metal isocyanate or, atelevated temperature, with urea, whereupon ring closure takes place. The6-nitro-2,4-dioxo-1,2,3,4-tetrahydroquinazolines or their n-alkylatedanalogs thus obtained, are converted into amino compounds with the aidof a suitable method, for example catalytic reduction, and then thedesired acetoacetylamino compounds are prepared therefrom by means ofsuitable reactants, for exam ple by reaction with diketene. It is alsopossible to start from anthranilic acid, or N-alkylated anthranilicacids, such as N-methyl-anthranilic acid, N-ethyl-anthranilic acid,N-i-propyl-anthranilic acid or N-i-butyl-anthranilic acid and to effectring closure as disclosed above by reaction with alkali metal isocyanateor urea, then to nitrate and finally to convert the6-nitro-2,4-dioxo-1,2,3,4-tetrahydroquinazolines thus obtained into thedesired acetoacetylamino compounds in the manner specified above.

The coupling reaction can be carried out in known manner, especially inan aqueous medium, where required in the presence of non ionic, anionactive or cation active dispersing agents.

To obtain an especially favorable crystal structure the coupling mixtureis advantageously heated for some time, for example at boilingtemperature or under pressure at temperatures above 100 C., whererequired in the presence of organic solvents, such as dichlorobenzene ordimethylformamide or resin soap. Especially pure and fast dyeings areobtained with the dyestuffs of the invention by after-treating the dyes,after coupling, in the form of moist filter cakes or dry powders withorganic solvents, such as pyridine, dimethylformamide, alcohol, glycol,glycol-monomethyl ether, glacial acetic acid, chlorobenzene,dichlorobenzene, or nitrobenzene, at reflux temperature or underpressure at elevated temperature or by grinding them in the presence ofgrinding auxiliaries.

The dyestuffs may also be coupled in the presence of carrier substanceswhich are suitable for the preparation of color lakes.

The new pigment dyestuffs are suitable for the preparation of printinginks, color lakes and dispersion paints, for coloring natural rubber,plastic material and natural or synthetic resins. They are, moreover,suitable for the pigment printing on substrates, especially textilefibre materials or other plane structures, for example paper. Thedyestuffs may also be used for other purposes, for example in a finelydivided form for the dyeing of rayon made from viscose or celluloseethers or esters, polyamides, polyurethanes, polyglycol-terephthalatesor polyacrylonitrile in the spinning solution, or for the coloration ofpaper.

The dyestuffs can advantageously be processed in the above media inwhich they show a high tinctorial strength and very pure shades. Thedyeings are very fast to light, weather and migration and stable to theaction of heat and chemical substances, especially solvents.

The following examples serve to illustrate the invention, the parts andpercentages being by weight unless stated otherwise.

EXAMPLE 1 24.6 parts of 1-amino-2,5-dimethoxybenzene-4-sulfonic acidmethylamide were stirred for about 1 hour with 40 parts by volume of Nhydrochloric acid and 60 parts by volume of water. The mixture was thendiluted with 100 parts by volume of water and diazotized at 5 C. with 20parts by volume of 5 N sodium nitrite solution. The solution wasclarified with kieselguhr and the excess of nitrous acid, if any, waseliminated by means of amidosulfonic acid.

27.4 parts of 6-acetoacetylamino-2,4-dioxo-1,2,3,4-tetrahydroquinazolinewere stirred at 20-25 C. with 200 parts by volume of water and themixture was dissolved by adding 30 parts by volume of 10 N sodiumhydroxide solution. After clarification with active carbon, the solutionwas diluted with 100 parts by volume of water, 20 parts by volume of a10% aqueous solution of a reaction product of about 20 mols of ethyleneoxide and 1 mol of stearyl alcohol were added and the coupling componentwas precipitated by adding 20 parts by volume of glacial acetic acid.

While maintaining the pH of about'5.5 constant, the diazonium saltsolution was introduced while carefully stirring at about 20 C. intothis solution of the coupling component. Coupling was rapidly complete.The coupling mixture was heated at the boil, suction-filtered hot,carefully washed with water andd tied at 65 C.

The yellow pigment obtained was powderized and heated for 2 hours to C.with 400 parts by volume of dimethylformamide. The mixture was thensuction-filtered, the dimethylformamide was washed olf with methanol andwater and the dyestuff was dried. A yellow pigment having a soft grainand a very pure shade was obtained. When incorporated in polyvinylchloride, a lacquer, a printing ink or a dispersion paint, the dyestuffyields pure yellow dyeings having a high fastness to light, a very highfastness to overvarnishing and an unobjectionable fastness to bleedingin polyvinyl chloride and a very good resistance to heat.

When 6 acetoaceylamino-Z,4-dioxo-1,2,3,4-tetrahydroquinazoline wasreplaced by an equivalent amount of 7-methyl-6-acetoacetylamino-2,4-dioxo-1,2,3,4 tetrahydroquinazoline or8-chloro-6-acetoaceylamino-2,4-dioxo-1,2, 3,4-tetrahydroquinazoline orS-chloro-d-acetoacetylamino- 2,4-dioxo-l,2,3,4-tetrahydroquinazoline,yellow dyestuffs having similar properties were obtained.

When 67 parts of polyvinyl chloride, 33 parts of a plasticizer mixtureof equal parts of dioctylphthalate and dibutylphthalate, 2 parts ofdibutyl-tin dilaurate', 0.5 part of titanium dioxide and 0.1 part of theabove dyestuif are mixed for 15 minutes at 150 C. on a roller device andthe mixture was processed into a sheet, the yellow coloration thereof isdistinguished by a very good color intensity, an excellent fastness toheat and migration and a very good fastness to light.

EXAMPLE 2 35.8 parts of l-amino-2,5-dimethoxybenzene-4-sulfonic acidB-naphthylamide were introduced into a mixture heated to 60 C. andconsisting of 40 parts by volume of 5 N hydrochloric acid and 60 partsby volume of water. The mixture was diluted with parts by volume ofwater and diazotized at 0-5 C. with 20 parts by volume of 5 N sodiumnitrite solution. Subsequently, further 1500 parts by volume of waterwere added and the solution was clarified with kieselguhr. An excess ofnitrous acig, if any, was eliminated by means of amidosulfonic aci Thisdiazonium salt solution was introduced while carefully stirring at about20 C. into a suspension of the coupling component in acetic acid, whichwas prepared as follows: 28.9 parts of G-acetoacetylamino-l-methyl-2,4-dioxo-l,2,3,4-tetrahydroquinazoline were dissolved at 20- 25 C., whilestirring, in a mixture of 200 parts by volume of water and 30 parts byvolume of 10 N sodium hydroxide solution. After clarification withactive carbon, this solution was introduced, within about 30 minuteswhile carefully stirring, into solution of 300 parts by volume of water,41 parts by volume of glacial acetic acid and 40 parts by volume of 10 Nsodium hydroxide solution to which 20 parts by volume of a 35% aqueoussolution of a reaction product of about 30 mols of ethylene oxide and 1mo] of oleyl alcohol had been added.

Coupling was complete very rapidly. The coupling mixture was heated atthe boil, suction-filtered, carefully Washed with water and dried at 65C.

The yellow pigment thus obtained having a high tinctorial strengthprovides dyeings having the same very good fastness as those obtainedwith the dyestuff of Ex- EXAMPLE 3 23.2 parts of1-amino-2,5-dimethoxybenzene-4-sulfonic acid amide were stirred forminutes with 50 parts by volume of glacial acetic acid. The mixture wasthen diazotized at C. with the equivalent amount of nitrosylsulfuricacid, stirring was continued for 30 minutes, the mixture was poured on400 parts by volume of ice water, clarified with kieselguhr and excessnitrous acid, if any, was destroyed by means of amidosulfonic acid.

In the manner disclosed in Example 1, the suspension of the couplingcomponent was prepared from 31.8 parts of6-acetoacetylamino-1-n-propyl-2,4-dioxo-l,2,3,4 tetrahydroquinazoline.

Coupling was also effected as disclosed in Example 1.

The dry dyestuff powder obtained was refluxed for 1.5 hours with 450parts by volume of glacial acetic acid, the mixture was thensuction-filtered, washed with methanol and water until the glacialacetic acid was eliminated, and dried at 65 C.

The pigment obtained provides yellow dyeings which practicallycorrespond to the pigment dyeings produced according to Example 1 asregards their fastness properties.

EXAMPLE 4 26.0 parts of 1-amino-2,S-dimethoxybenzene-4-sulfonic acidethylamide were diazotized as disclosed in Example 1.

The preparation of the suspension of the coupling component and couplingwere carried out as disclosed in Example 2.

The filter cake of the dyestuff obtained after suctionfiltration' washeated for 6 hours to 125 C. in a pressure vessel with a mixture of 600parts by volume of alcohol and 360 parts by volume of water. The mixturewas then suction-filtered, carefully washed with water and dried at 65C.

The dyeings produced with the yellow pigment thus obtained arepracticaly identical with those produced in Example 1 as regards theirfastness properties.

EXAMPLE 5 33.6 parts of 1-amino-2,5-diethoxybenzene-4-sulfonic acidanilide were diazotized as disclosed in Example 1.

The suspension of the coupling component was prepared according toExample 2. Coupling was also efiYected as disclosed in Example 2, butthe mixture was not suction-filtered when coupling was complete. Thecoupling mixture was heated to 125 C. for 5 hours in a pressure vessel,then suction-filtered, carefully washed with water and dried at 65 C.

The dyestuff obtained yields yellow dyeings which practically have thesame fastness properties as the pigment prepared according to Example 1.

The following table contains a number of further yellow pigmentdyestuffs which can be prepared in a manner analogous to that disclosedin Examples 1 to 5 R1 Ra a H CrHs H H CH3 CH3 CH3 CaHs H CH: CzHs CH3CH3 1'1-C H7 CzH5 CH3 CH3 CH3 3 CH Il-CgHy CH3 CH3 n-C4H C2H5 Il-C4HoCH3 n-O1H1 C2H5 C2 s 1-C3H7 CH3 CH3 H CH3 CH3 CaHs CH H CaHs CH3 CH3gags -Ca 1 a 5 1 '-C H engoflrrs 0 H; H 3 7 CH2CaH C2H5 CH3 CH3 CH3 CH3ClHa n-CaH7 n-CaH? ([3 Fa CiHs H I C F CH CH a 1 l? 02 4 u 2 5 (i) C HaC 2H5 Il-CaH7 N02 CH3 H 3 C H CH -C a H C1 13 CH C H -C H H C 8 2 a I1 37 CH3 H H H 11-C4H9 CH Cl Ha TABLEContinued R; Ra Ra n-C H H CH3 CH3n-C4H9 (32H; H S:C:Ha

( 31 OH; H

B43411: CiHs CFz- $014311;-

We claim: 1. A dyestufi of the formula 1 I 0R2 0--N oo RiNHS0N=N(])HCONH-N A COCH a wherein R is hydrogen, lower alkyl, phenyl,naphthyl, benzyl, diphenyl, phenoxyphenyl, phenyl-sulfo-phenyl,benzyl-sulfo-phenyl, cyclohexyl, or phenyl mono-, dior tri-substitutedby lower alkyl, lower alkoxy, trifluoromethyl, halogen, nitro, or acombination thereof, or cyclohexyl monoor (ii-substituted by loweralkyl, halogen or a combination thereof, R is lower alkyl, R is hydrogenor lower alkyl, R is hydrogen, lower alkyl, lower alkoxy or halogen andn is 1 or 2.

2. A dyestuff of the formula wherein R is hydrogen, lower alkyl, phenyl,naphthyl, benzyl or cyclohexyl substituted by 1 to 3 members selectedfrom the group consisting of chlorine, bromine and lower alkyl, R islower alkyl, R is hydrogen or lower alkyl, R is a hydrogen, chlorine,bromine, lower alkyl or lower alkoxy, and n is 1 or 2.

3. The dyestuif of the formula CH3 OCHz O I (II-=0 g 5 oHaHN01s-@N=Norroo-NH-' 0:0 CH3 \N/ 4. The dyestulf of the formula on 00113 g a hCHaHNO;S N==N( JH-C O-NH 0' 0 5. The dyestuif of the formula OH 00m A a01 R 1 =0 1 omnNois- =N-orr -o O--NH OCH; /('J=O 6. The dyestutf of theformula OH OCH; 5 3 O 1 =0 5 oH3HNozs-@N=N orr o0NH CH3 /&=O

7. The dyestulf of the formula 0 00m O i 4 omrmms- N=NGH-O O-NH-- OCH3 NH References Cited UNITED STATES PATENTS 3,113,938 10/1963 Nakaten eta1. 260204 3,118,870 1/1964 Dietz et a1. 260-154 LEWIS GOTTS, PrimaryExaminer D. M. PAPUGA, Assistant Examiner US. Cl. X.R. 260-208, 256.4

